GB629019A - New polymerisable materials and polymers thereof - Google Patents

Abstract

Polymerizable compounds having more than two unconjugated CH2=C< groups are produced by reaction of an alcohol having three or more hydroxyl groups with one or more chloroformates of acrylic, methacrylic and/or a -haloacrylic monohydroxy esters of di- or polyhydric alcohols. The products have the formula [(CH2=CX.CO.O)mR.O.CO.O]nZ, where m is an integer, n is an integer greater than 2, Z is an organic radical of valency n, R is an organic radical of valency m+1, and X is hydrogen, methyl or halogen. The reactants should have a content of acrylic groups calculated as hydroxyl groups of less than 25, preferably less than 17, or less than 12.5, preferably less than 8.5, or greater than 3.5 per cent by weight of said compounds minus their weight of acrylic groups and the weight of the by-products of the reaction to obtain preferred polymers. Polyhydric alcohols for reaction with the chloroformates include glycerol, pentaerythritol, and soluble derivatives of cellulose and polyvinyl alcohol, e.g. cellulose diacetate and ester, ether, and/or acetal derivatives of polyvinyl alcohol. Reaction is preferably effected below 40 DEG C. in the presence of a solid base, e.g. sodium carbonate. Polymerization inhibitors may be present. If hard polymers are desired, excess polyhydric alcohol should be removed and production of ethylene carbonate prevented. Polymerization may be effected in stages, in the presence of small amounts of inhibitors, and of compounds containing C = C linkages which may or may not react with the compounds of the invention, e.g. di(allyl glycollyl) succinate, methacrylates, vinyl compounds, maleic anhydride and polyesters of maleic or fumaric acid and dihydric alcohols. The compounds may be used for production of laminated sheets of fibrous materials. In examples: (1) ethylene glycol, trichlorethylene, and hydroquinone disulphonic acid are heated and air bubbled through, methacrylic acid being added when refluxing commences, and water removed as an azeotrope. The product is treated with sodium carbonate, filtered, the filtrate washed with brine, and the solvent then evaporated to give hydroxy ethyl methacrylate. This is converted with phosgene and the chloroformate treated with glycerol and sodium carbonate and worked up to yield glycerol tris (methacryloxy ethyl carbonate); (2) pentaerythritol replaces the glycerol of (1) to give pentaerythritol tetrakis (methacryloxy ethyl carbonate); (3) to (6) the products are mixed with benzoyl peroxide or a solution thereof in butyl methacrylate and polymerized after application to sheets of glass fibre cloth, canvas or Kraft paper to form laminated material or alone to form sheets for map covers.ALSO:Polymerizable compounds having more than two unconjugated CH2=C< groups are produced by reaction of an alcohol having three or more hydroxyl groups with one or more chloroformates of acrylic, methacrylic and/or a -haloacrylic monohydroxy esters of di- or polyhydric alcohols. The products have the formula [(CH2=CX.CO.O)mR.O.CO.O]nZ, where m is an integer, n is an integer greater than 2, Z is an organic radical of valency n, R is an organic radical of valency m+1, and X is hydrogen, methyl or halogen. The reactants should have a content of acrylic groups calculated as hydroxyl groups of less than 25, preferably less than 17, or less than 12.5, preferably less than 8.5, or greater than 3.5 per cent by weight of said compounds, minus their weight of acrylic groups and the weight of the by-products of the reaction to obtain preferred polymers. Chloroformates of half esters of dihydric alcohols may be prepared from phosgene and the half esters. The latter may be prepared from the acrylic acid, its lower esters, anhydride or acid chloride, and a polyhydric alcohol, or from its salts, and a hydroxy chloride such as ethylene chlorhydrin. Partial esters of various glycols, glycerol, and pentaerythritol are specified. Polymerization inhibitors, preferably those described in Specification 606,685, may be present, and azeotroping liquids added to remove water or alcohol during esterification. Polyhydric alcohols for reaction with the chloroformates include glycerol, pentaerythritol, and soluble derivatives of cellulose and polyvinyl alcohol, e.g. cellulose diacetate and ester, ether, and/or acetal derivatives of polyvinyl alcohol. Reaction is preferably effected below 40 DEG C. in the presence of a solid base, e.g. sodium carbonate. Polymerization inhibitors may be present. If hard polymers are desired, excess polyhydric alcohol should be removed and production of ethylene carbonate prevented. Polymerization may be effected in stages, in the presence of small amounts of inhibitors, and of compounds containing C=C linkages which may or may not react with the compounds of the invention, e.g. di(allyl glycollyl) succinate, methacrylates, vinyl compounds, maleic anhydride and polyesters of maleic or fumaric acid and dihydric alcohols. The compounds may be used for production of laminated sheets of fibrous materials. In examples: (1) ethylene glycol, trichlorethylene, and hydroquinone disulphonic acid are heated and air bubbled through, methacrylic acid being added when refluxing commenced, and water removed as an azeotrope. The product is treated with sodium carbonate, filtered, the filtrate washed with brine, and the solvent then evaporated to give hydroxy ethyl methacrylate. This is converted with phosgene and the chloroformate treated with glycerol and sodium carbonate and worked up to yield glycerol tris(methacryloxy ethyl carbonate); (2) pentaerythritol replaces the glycerol of (1) to give pentaerythritol tetrakis (methacryloxy ethyl carbonate); (3) to (6) the products are mixed with benzoyl peroxide or a solution thereof in butyl methacrylate and polymerized after application to sheets of glass fibre cloth, canvas or Kraft paper to form laminated material or alone to form sheets for map covers.